PAPER www.rsc.

org/softmatter | Soft Matter

The preferential deposition of silica micro-particles at the boundary of inkjet

printed droplets
Jolke Perelaer,ab Patrick J. Smith,†b Chris E. Hendriks,ab Antje M. J. van den Bergab and
Ulrich S. Schubert*abc
Received 2nd October 2007, Accepted 24th January 2008
First published as an Advance Article on the web 10th March 2008
DOI: 10.1039/b715076h

The deposition behaviour of uniformly sized silica particles in drying aqueous droplets has
been investigated for a range of particle sizes, 0.33, 1, 3 and 5 mm, in order to gain an improved
understanding of the coffee drop effect. The droplets were produced by inkjet printing, which
allowed multiple droplets of similar volume to be studied. Our observations show that particle size
and the contact angle formed by the solvent droplet with the substrate determine how close to
the boundary a particle is deposited. After drying, it was found that if the contact angle was less
than 90
, smaller particles were located closer to the original droplet’s periphery than larger particles
in similar sized droplets. This deposition of particles can be explained by the wedge shape of the
drying droplet’s edge, which physically limits the movement of particles towards the droplet’s
periphery. In this paper we show that the size of a suspended particle influences the final dried
morphology of a printed feature.

Introduction have been investigated, e.g. for their self-assembly properties

Although, the behaviour of a liquid on a substrate is generally
well-understood,1,2 the behaviour of either a solution or a suspen-
sion on a substrate continues to stimulate debate.3–5 An often
seen phenomenon is that droplets of solutions and suspensions
dry in such a fashion that the dried material forms a ring. Deegan
et al.3a gave three conditions for ring formation: the solvent
meets the substrate at a non-zero contact angle, the solvent
evaporates, and the contact line is pinned to its original position.
The coffee drop effect is named after the commonly observed
dark coloured rings of dried coffee droplets. Deegan explained
the appearance of these and other rings as being caused by a
replenishing flow, which originates in a drying droplet’s interior
and travels towards the substrate–air–liquid interface, i.e. the
contact line.3 The replenishing flow is a consequence of evapora-
tion occurring at the contact line, which is pinned. Therefore, as
solvent evaporates from the droplet, liquid is carried towards the
droplet’s boundary due to the contact line being unable to
retreat. The strength of the replenishing flow was demonstrated
by Magdassi et al. who found that a metallic ring, which had
formed at room temperature via the evaporation of an aqueous
droplet containing silver nanoparticles, exhibited high electrical
conductivity (up to 15% of that for bulk silver).6 Similarly,
colloidal systems consisting of monodisperse microspheres
a
Laboratory of Macromolecular Chemistry and Nanoscience, Eindhoven
University of Technology, P.O. Box 513, 5600 MB Eindhoven, The
Netherlands. E-mail: u.s.schubert@tue.nl; Fax: +31 40 247 4186
b
Dutch Polymer Institute (DPI), P.O. Box 902, 5600 AX Eindhoven, The
Netherlands
c
Laboratory of Organic and Macromolecular Chemistry, Friedrich-
Schiller-University Jena, Humboldtstr. 10, 7743 Jena, Germany
† Current address: Laboratory for Simulation, Albert-Ludwigs-University
Freiburg, Georges-Koehler-Allee 102, 79110, Germany.
upon evaporation of the solvent,7 and as photonic bandgap
materials.8 Furthermore, it was reported that in a drying droplet
containing a bi-modal particle population of 60 nm and 200 nm
sized polystyrene nanoparticles, the larger particles aggregated at
the border of the ring, whereas the smaller particles were found
as an inner ring nearer to the centre of the dried droplet.9
This observation is fascinating, but counterintuitive, because it
contradicts classical laws of movement: smaller particles are
easier to move than larger particles due to their smaller mass.
These results, however, could be used as a size exclusion separa-
tion technique, since particles are aggregating according to their
sizes.
The coffee staining effect is a frequently observed phenomenon
and can be seen in any application that deposits bodies of solution
or suspensions onto a relatively smooth surface; such as drop-
casting, spin-coating, and inkjet printing. In particular, the latter
technique has matured as a technique for depositing small
amounts of functional materials, for instance light-emitting
polymers and nanoparticles, in a precise and selective way onto
a wide range of substrates,10,11 and has been used for a number
of applications, e.g. the fabrication of polymer light-emitting
diodes and field effect transistors.12 The amount of waste that is
generated during processing is drastically reduced due to the
selective deposition of materials, which lowers the production
costs significantly. However, as a consequence of depositing
liquid onto a substrate, the coffee drop effect has been observed
in some inkjet printed features.13 The effect can be removed by
either using a solvent mixture system,14 which reduces the higher
evaporation rate at a liquid feature’s edge, or by making surface-
energy patterns, which direct the ink to predefined areas on the
substrate.15,16 Conversely, the coffee drop effect has also been
exploited as an advanced etching technique to create polymer-
relief microstructures by inkjet etching.17

1072 | Soft Matter, 2008, 4, 1072–1078 This journal is ª The Royal Society of Chemistry 2008
 The main advantage of inkjet printing is its ability to precisely
produce droplets with a consistent volume.18 Therefore, many
equally sized droplets can be printed in sequence and studied
in parallel allowing a statistical examination to be performed;
in contrast to earlier studies on the coffee drop effect whereby
only single droplets were investigated.3,5,6 In this contribution,
we observe the behaviour of aqueous droplets of colloidal
micron-sized particle systems on glass slides that have different
surface energy, as a result of different surface treatments. We
used single-sized silica microspheres with sizes ranging from
330 nm up to 5 mm; these were monodisperse particles to negate
the effect of gravitational force on particle deposition.9 An inkjet
printer was used to produce a series of equally-sized droplets,
which allowed us to reduce the error in the measurements and
significantly increase experimental reproducibility.
Experimental
Four batches of monodisperse silica microspheres with a poly-
dispersity less than 3% were obtained from Bangs Laboratories
Inc. (Fishers, IN, USA). The silica particles had hydroxyl or
silanol (Si–OH) surface groups and diameters of 0.33, 0.97,
3.01 and 4.74 mm, respectively. All colloidal suspensions were
diluted with ultra pure deionized water to 1 wt% prior to usage.
The substrates were commercially available microscope slides
(3  1 inch slides from Marienfeld, Lauda-Königshofen,
Germany) and were thoroughly cleaned by first washing with
sodium dodecyl sulfate solution, then rinsed with de-ionized
water, then washed with acetone and finally with isopropanol
before being dried under a flow of air. These substrates had
a contact angle of 20
(qA ¼ 30
, qR ¼ 10
). Hydrophobic
substrates were prepared by coating glass slides with octadecyl
trichlorosilane (OTS), which decreases the surface energy; the
contact angle was 103
(qA ¼ 110
, qR ¼ 95
).19 Hydrophilic
substrates were prepared by ashing the cleaned glass slides as
Fig. 1 Bright field optical microscopy images of a drying droplet of an aqueous suspension of 5 mm sized silica particles. The white arrow indicates the
water contact line, whereas the gray arrow points out the place where particles sediment. The time between each image is 2 s and the magnification was
250 times. Scale bar is 50 mm.
This journal is ª The Royal Society of Chemistry 2008
described before with O2 plasma in a plasma etcher (K1050X,
Emitech, Kent, UK), which increases the surface energy of the
glass; the contact angle was 5
. The glass slides for the second
printing experiments were cleaned by rinsing subsequently with
acetone and ethanol, followed by drying with an air gun; this
resulted in a contact angle of 25
(qA ¼ 34
, qR ¼ 15
). The
advancing and receding contact angles were measured using
a Dataphysics OCA 30 (Filderstadt, Germany).
Inkjet printing was performed using an Autodrop system
(Microdrop Technologies, Norderstedt, Germany). This system
was fitted with a 70 mm printhead, which can be moved in the
z-direction. The glass slides were placed onto a platen that can
move in x- and y-direction. The Autodrop system has a
positioning accuracy of 1 mm and a stroboscopic video camera
set-up to investigate and optimize droplet formation. For the
first setup of printing experiments (Table 1), a MD-K140 head
was used with printing parameters of 85 V, 200 Hz and a pulse
width of 30 ms. The second printing series (Table 2) were
performed using a MD-K-130 head with printing parameters
of 47 V, 200 Hz and a pulse width of 57 ms. All samples were
printed at room temperature.
Optical and scanning electron microscopy (SEM) images were
taken using optical microscopy (Axioplan Imaging 2, Zeiss,
Germany) and a FEG E-SEM XL30 (Philips, Eindhoven, The
Netherlands).
Results and discussion
Coffee drop effect with monomodal silica particles
A series of experimentation was performed to observe how parti-
cles behave at the contact line, using drop-cast monodisperse
suspensions of silica particles. Fig. 1 shows optical microscopy
images of the edge of a drying droplet of an aqueous suspension
of 5 mm silica particles on a cleaned glass substrate. The beha-
viour of the thirteen particles enclosed in the boxes is of interest.
Soft Matter, 2008, 4, 1072–1078 | 1073

Fig. 2 Schematic representation of the situation at the contact line
where microspheric particles segregate at different positions. Particle
sizes are not drawn to scale, and q indicates the contact angle the liquid
forms with the substrate.
In the left image, the thirteen particles can be seen to form three
groups. These particles combine into a larger cluster over time
(6 s), as illustrated by the images moving from left to right. It
can be seen that the particles are not positioned at the contact
line and although they are unable to move back into the bulk
of the droplet, due to the replenishing flow, they are able to
move parallel to the contact line.
Fig. 2 illustrates the dependence of the particle’s sedimentation
on the contact angle formed by the solvent with the substrate.
Particles with a larger diameter end up further from the contact
line, i.e. nearer the droplet’s centre, than smaller sized particles.
This theory was tested experimentally and is discussed in the next
section.
Particle size dependency in the coffee drop effect of inkjet printed
suspensions
The investigations into the behaviour of differently sized parti-
cles at the periphery of a drying droplet were performed using
inkjet printing, which produces droplets of equal volumes.18a
This allowed the creation of a matrix consisting of 10  10 drop-
lets of equal volumes. From these 100 drops, 7% were identified
as imperfect droplets on account of having an elliptical shape,
which may have formed due to chemical or physical imperfec-
tions on the substrate, and were discounted. For each sample,
10 droplets were characterized by measuring their diameters in
both the x- and y-directions, with the averaged diameter per
droplet being used for further calculations.
Four aqueous monomodal particle suspensions, with particle
diameters (their radii are given in parentheses) of 0.33 (0.165),
0.97 (0.485), 3.01 (1.505) and 4.97 (2.405) mm, were inkjet printed
onto cleaned glass slides. All of the suspensions were deposited at
room temperature, using the same printer settings to ensure that
the droplet diameter (65.3 mm) and therefore the volume (147 pL)
of each droplet was the same. It was expected that only particles
with sizes below 3.5 mm would be printable, since the printhead’s
nozzle diameter was 70 mm. As a general rule, particles that are
greater than 5% of the orifice diameter will cause some instability
in the drop generation behavior.20 However, no problems with
clogging were observed when printing the larger 5 mm particles.
(To the casual reader, the fact that a 5 mm particle passes through
1074 | Soft Matter, 2008, 4, 1072–1078
a 70 mm nozzle may not seem remarkable.) Two explanations
are offered for the successful printing of the larger particles.
Firstly, the concentration of the suspension is very low, only
1 wt%. Therefore, the chance of particles clustering to form
agglomerates is reduced. The second explanation is that the silica
microspheres are not functionalized and the surface groups are
hydroxyl or silanol (Si–OH), which show a low tendency for
agglomeration.
Fig. 3 shows selected dried droplets that were obtained for the
four inks. It can be seen that droplets of suspensions containing
smaller sized particles leave a larger dried droplet on the surface
after drying. These sizes can be explained in terms of the contact
angle that the solvent formed and the ability of a particle to
approach the contact line. The shape of a solvent droplet’s
edge on a substrate can be thought of as a triangular wedge, as
shown in Fig. 2. The contact angle of the droplet on a substrate
limits the place of sedimentation of the particles within the
droplet. The larger the particles are, the greater the distance
will be between these particles and the initial contact line. There-
fore, the diameter of a dried droplet decreases with increased
particle size since larger particles cannot travel as near to the
contact line as smaller particles.
The same jetting parameters were used for the inkjet printed
droplets of all four silica microsphere 1 wt% suspensions; there-
fore we assume that volumes of the droplets are equal. If we
simplify the edge of the droplet to the triangle shown in the inset
of Fig. 4, we can calculate the distance from a deposited particle
to the contact line by using a simple tangent equation:
r
x¼ (1)
tanðq=2Þ
where x represents the distance between the contact line and the
centre of the particle, which is sitting on the surface; r is particle
radius and q the contact angle that the solvent forms with the
substrate.
Fig. 3 Bright field microscopy images of inkjet printed droplets of
aqueous suspensions containing 0.33 mm (a), 1 mm (b), 3 mm (c) and
5 mm (d) sized silica particles. The photograph that shows the 3 mm
particle (c) has the focus point on the contact line rather than on the
particles.
This journal is ª The Royal Society of Chemistry 2008

Fig. 4 Phase contrast microscopy images of inkjet printed droplets of an
aqueous suspension containing 3 mm sized silica particles. The white
arrow shows the contact line of the liquid, whereas the black arrow indi-
cates the position where the particles sediment. The inset shows a close-
up, where r is the radius of the particle, x the distance from the particle to
the contact line, and q the contact angle of the droplet with the substrate.
Extrand recently presented a relationship between the contact
angle, the cross-sectional area and the volume of a sessile liquid
droplet.21 From his equations, a formula for the contact
diameter as a function of the droplet diameter before impact
and the contact angle can be derived (the appendix shows the
complete derivation):
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
3 4
Dðq; dÞ ¼ d sin q
ð1  cos qÞ2 ð2 þ cos qÞ
where D represents the contact diameter of the deposited droplet
sitting on the surface, and d is the in-flight droplet diameter.
From Fig. 4, a relationship can now be derived, where the dried
droplet diameter, a can be written as a function of contact
diameter and contact angle:
 
2r
a ¼ D  2x ¼ D  (3)
tanðq=2Þ
This makes it possible to compare the calculated dried
droplet diameter to the measured value obtained from the
experiments.
Table 1 shows the measured and calculated values of a for all
four particle radii. The values for the measured contact droplet
diameters deviate within 7% from the calculated values. The
error in the dried droplet diameter increases with larger particle
sizes. It is expected that these values vary with particle size, since
the distance from the actual position of the particle and the edge
of the droplet increases with increasing particle size. The assump-
tion is also made that all of the droplets produced by the inkjet
printer are uniform.18 However, it is possible that slight varia-
tions occurred, e.g. a small fluctuation in the holding pressure,
which produced variably sized droplets.
The experiments mentioned before were all performed on
cleaned glass slides.22 Therefore the contact angle had a constant
value of 20
, with an advancing contact angle (qA) of 34
and
a receding contact angle (qR) of 15
. The contact diameter in
This journal is ª The Royal Society of Chemistry 2008
Table 1 Particle size dependency of the dried droplet features; where r is
the particle radius, q is the contact angle of the liquid with the substrate,
D is the contact diameter as calculated from eqn (2), x the distance from
the placement of the particles to the original contact line of the droplet
that is calculated from eqn (1), acalculated the calculated droplet diameter
from eqn (3), and ameasured the measured droplet diameter from the inkjet
printed droplets. The droplet in-flight diameter was 65.3 mm and its
calculated volume was 147 pL
r/mm q (
) D/mm x/mm acalculated/mm ameasured/mm
0.165 20 160.6 0.9 158.8 171  4
0.485 20 160.6 2.7 155.2 160  4
1.505 20 160.6 8.3 144.0 134  3
2.485 20 160.6 13.7 133.2 128  11
eqn (2) shows approximately an exponential decay with the
contact angle, which has been observed in the literature
previously.13c The contact diameter will be large for small contact
angles and vice versa. Therefore, it is interesting to also investi-
gate the effect of varying the contact angle on the dried droplet
diameter, which is discussed in the following section.
The effect of contact angle on the position of suspended silica
particles
In order to investigate the effect of varying the contact angle on
the placement of the particles on the substrate, suspensions of
silica particles with different particle sizes were inkjet printed
onto glass substrates, whose surface energy had been modified.
Firstly, droplets were inkjet printed onto glass slides that were
(2)
cleaned following a slightly altered procedure: rinsing with
acetone, rinsing with ethanol and subsequently drying with an
air gun. Using ethanol rather than isopropanol and by skipping
the washing step, with sodium dodecyl sulfate solution, slightly
decreases the wettability of the glass slides. The contact angle
was found to be 25
(qA ¼ 34
, qR ¼ 15
). Secondly, glass slides
cleaned as described above were coated with an OTS monolayer,
which renders the substrate hydrophobic.23 The contact angle
was measured to be 103
(qA ¼ 110
, qR 95
). As a third
substrate, the cleaned glass slides were ashed with O2 plasma,
which increases the hydrophilicity of glass. The contact angle
of the substrate was approximately 5
. Here, the advancing
and receding contact angles were too low to measure.
Three silica particle suspensions were printed using the same
printer settings. The in-flight droplet size was 73.2 mm and the
calculated volume was subsequently determined to be 205.4
pL. The difference between droplet volumes produced in this
set of experiments and those reported earlier is due to a different
printhead being used. Again matrices of 10  10 were printed, of
which less than 10 droplets were rejected due to having
non-circular geometries. From 10 droplets, the diameter both
horizontally as well as vertically was measured.
In Fig. 5 and Table 2 the results of inkjet printed droplets on
substrates with different contact angles are shown. In the
previous section, it was shown that when the particle size was
decreased the dried droplet features have a larger diameter
(Fig. 5b). This trend can be also observed for particles on
a high surface energy (low q) substrate, as depicted in Fig. 5a.
However, when the contact angle is increased to 90
or higher
Soft Matter, 2008, 4, 1072–1078 | 1075
Table 2 Contact angle and particle dependency of the dried inkjet printed droplet features. In the top columns different contact angles are shown: OTS
is a glass substrate coated with an OTS monolayer, cleaned glass is simply cleaned glass, and plasma treated glass is rendered hydrophilic by using
plasma ashing (see Experimental part). In the first column, r represents the particle radius, D is the contact diameter as calculated from eqn (2), x is
the distance from the placement of the particles to the original contact line of the droplet calculated from eqn (1), acalculated the calculated dried droplet
diameter from eqn (3), and ameasured is the measured dried droplet diameter from the inkjet printed droplets. All values are displayed in mm. The droplet
in-flight diameter was 73.2 mm and its calculated volume was 205 pL

OTS (q ¼ 103
) Cleaned glass (q ¼ 25
) Plasma treated glass (q ¼ 5
)

r D x acalculated ameasured D x acalculated ameasured D x acalculated ameasured

0.165 81.7 0.2 81.3 28.7  2 168.4 0.8 166.8 172.3  3 310.4 4.7 301.0 307.1  5
0.485 81.7 0.7 80.3 31.4  2 168.4 2.2 164.0 143.8  4 310.4 13.9 282.6 299.9  5
1.505 81.7 2.1 77.5 40.9  3 168.4 6.9 154.6 123.4  4 310.4 43.1 224.2 232.4  3

the discrimination of particle size vanishes and all particle sizes
show a similar dried droplet diameter on a substrate with
a low surface energy (Fig. 5c). This observation corresponds to
that of Moon et al.7
Scanning electron microscopy (SEM) was used to look closer
at the printed three-dimensional features on OTS coated glass
substrates. Fig. 6a–c show the polycrystalline formation of the
particles, even for small grain sizes. Furthermore, it was
observed that with increasing particle size the dried droplet
feature increases as well. Since each particle suspension was
printed with equal weight percentages of solid material, and all
silica particles have equal density, an increase in the dried droplet
diameter is observed due to the fact that larger sphere shaped
particles leave more unoccupied volume—i.e. holes—in their
close-packed structure. The stapling is not ideal and therefore
it cannot be assigned to be either hexagonal close-packing or
cubic close-packing. Nevertheless, equally sized spheres with
radius r packed into a three-dimensional structure create holes
that have an unoccupied volume for spheres not larger than
0.414r (for an octahedral hole) or 0.225r (for a tetrahedral
hole).24
Furthermore, when calculating the total volume of the inkjet
printed particles and comparing that value to the volume of
the hemisphere formed after drying (calculated from the
measured dried droplet diameter) the deviation for large particles
between measured and observed volume is larger than for small
particles, as shown in Table 3 (last column; packing factor). This
was expected and observed previously in the literature,7b since

Fig. 5 Phase contrast microscopy images of inkjet printed droplets of aqueous suspensions of silica particles on high surface energy substrates (a),
cleaned glass slides (b), and low energy substrates (c). Each row shows, from left to right, a particle size of 0.33 mm, 1 mm and 3 mm, respectively.

1076 | Soft Matter, 2008, 4, 1072–1078 This journal is ª The Royal Society of Chemistry 2008
 the drying droplet, which physically limits the ability of the
larger particles to move nearer to the periphery. If the contact
angle is 90
or higher, this discrimination of particle size no
longer occurs.

Appendix
In his Langmuir paper21 Extrand derives two formulas, eqn (4)
and eqn (5), for the maximum cross-sectional area A:

A ¼ (3V/p)2/3(q – cosq sinq)[(1 – cosq)2(2 + cosq)]2/3 (4)

A ¼ (1/4)D2(q – cosq sinq)/sin2q (5)

where V is the droplet volume, q the contact angle with the

substrate and D the contact diameter. Substituting eqn (5) into
Fig. 6 Scanning electron microscopy (SEM) images of silica particles eqn (4) gives:
with a particle diameter of 0.33 mm (a), 1 mm (b) and 3 mm (c) on OTS
coated glass slides. (1/4)D2/sin2q ¼ (3V/p)2/3[(1 – cosq)2(2 + cosq)]2/3 (6)

D2 ¼ 4sin2q(3V/p)2/3[(1 – cos q)2(2 + cosq)]2/3 (7)

the packing of large particles is less efficient than the packing of
small particles, when the initial droplet volume remained the With
same.
V ¼ (4/3)pR3 ¼ (1/6)pD3 (8)

Conclusion this equation can be recombined and simplified:

We expand upon the investigations into the coffee drop effect,
published earlier by Deegan, where it was written that solute D ¼ 2sinq (1⁄2 d3)1/3[(1 – cosq)2(2 + cosq)]1/3 (9)
does not influence the observed final features, which has led to
the popular explanation that material always sediments at the Where d is the droplet diameter before surface impact. Finally,
contact line. We have shown that suspended media play a part we can write this as:
in the final feature size by depositing as close as possible to the sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
contact line. 3 4
Dðq; dÞ ¼ d sin q (2)
We have used an inkjet printer to produce an array of ð1  cos qÞ2 ð2 þ cos qÞ
uniformly sized droplets, which were composed of monodisperse
silica microspheres suspended in water, and observed an influ- Eqn (2) describes the contact diameter as a function of contact
ence on the final dried droplet diameter as a consequence of angle and initial droplet diameter.
particle size. We found that for larger particles there was a greater
difference between initial droplet diameter and the dried droplet
diameter. The distance between the contact line and the
Acknowledgements
deposited particles, which make up the dried droplet, depends
on the contact angle that the solvent forms with the substrate The authors would like to thank Thijs van Osch for the contact
and the size of the suspended particles. This preferential angle measurements and the Dutch Polymer Institute for finan-
deposition of particles is caused by the wedge-shaped dome of cial support (project #546).

Table 3 Packing efficiency for silica microspheres with different particle radii r. The second column shows the number of particles per mL, obtained
from the supplier of the particles. The number of particles on the surface shows the amount of particles within one inkjet printed droplet, and subse-
quently the total particle volume is the number of particles multiplied by their own volume. The droplet volume shows the volume of the half hemisphere
formed at the surface, calculated from the measured feature diameter on the substrate. Finally, the packing factor is the ratio of the total particle volume
to the droplet volume

Number of particles Total particle

r/mm Particles per mL printed on the surface volume/pL Droplet volume/pL Packing factor (%)

0.165 2.797  1012 569 749 10.7 12.3 87

0.485 1.101  1011 22 427 10.7 16.1 66
1.505 3.608  109 733 10.5 17.9 59

This journal is ª The Royal Society of Chemistry 2008 Soft Matter, 2008, 4, 1072–1078 | 1077
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This journal is ª The Royal Society of Chemistry 2008